CN105200458A - Method for preparing titanium carbide - Google Patents
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- CN105200458A CN105200458A CN201510705230.2A CN201510705230A CN105200458A CN 105200458 A CN105200458 A CN 105200458A CN 201510705230 A CN201510705230 A CN 201510705230A CN 105200458 A CN105200458 A CN 105200458A
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Abstract
The invention belongs to the field of preparation of inorganic non-metallic materials, and concretely relates to a method for preparing titanium carbide. The to-be solved technical problem is to provide the method for preparing titanium carbide. The method comprises the following steps: a, preparing low-valence titanium, concretely, reacting sponge titanium with titanium tetrachloride in molten salts of sodium chloride and potassium chloride, so as to prepare a low-valence titanium electrolyte; and b, preparing titanium carbide, concretely, taking sponge titanium as an anode and graphite as a cathode, performing electrolysis in the low-valence titanium electrolyte obtained in the step a, and precipitating titanium on the cathode, so as to obtain titanium carbide on the cathode after the metal titanium is reacted with graphite. The method is capable of preparing titanium carbide, and possesses the advantages of low cost, short time, high product purity and the like.
Description
Technical field
The invention belongs to ceramic preparation field, be specifically related to a kind of method preparing titanium carbide.
Background technology
Titanium carbide (TiC) has very high chemical stability, work hardly with general acid, also be simultaneously typical transition metal carbide, there is high rigidity, high-melting-point, the series of advantages such as wear-resistant and be applied to making the fields such as pottery, mechanical workout, metallurgical mineral products, aerospace.At present, the method preparing titanium carbide powder both at home and abroad mainly contains carbothermic reduction TiO
2method, direct reaction method, sol-gel method etc.At present, the too high meeting of temperature of reaction of direct reaction method causes high temperature sintering phenomenon and product particle size is comparatively large, and sol-gel method synthesis technique is complicated, and dry shrinkage is comparatively large, is difficult to industrialization.The industrial main method preparing titanium carbide is: in tube furnace or resistance furnace, reduce TiO with carbon black
2powder and obtain TiC powder, but need high temperature (1700 ~ 2100 DEG C) and long soaking time (10 ~ 24h) because of this method, product easily occurs that bulk is reunited, particle shape is uneven, there is the phenomenons such as unreacted raw material.Therefore fully mixing raw material, to reduce temperature of reaction and reaction times and prepare high-quality TiC powder be problem in the urgent need to address in research.It is low that electrolytic preparation titanium carbide has temperature of reaction, and the reaction times is short, can be met the powder requiring particle diameter, and have continous-stable advantages of higher, and domestic at present rarely have report.
Summary of the invention
For the shortcoming that above-mentioned prior art exists, goal of the invention of the present invention is to provide a kind of method preparing titanium carbide.The method has the advantages such as temperature of reaction is low, the reaction times is short, and the titanium carbide that the method prepares have purity higher than 99.9% technique effect.
Technical problem to be solved by this invention is to provide a kind of method preparing titanium carbide.The method comprises the following steps:
A, prepare Low-valent Titanium: react in the fused salt of sodium-chlor and Repone K with titanium sponge and titanium tetrachloride and prepare Low-valent Titanium ionogen;
B, prepare titanium carbide: take titanium sponge as anode, graphite is negative electrode, carry out electrolysis in the Low-valent Titanium ionogen of step a after, precipitating metal titanium on negative electrode, can obtain titanium carbide after this metal titanium and graphite react on negative electrode.
Preferably, above-mentionedly prepare in the method steps a of titanium carbide, described sodium-chlor and Repone K be with etc. mole to add.
Preferably, above-mentionedly prepare in the method steps a of titanium carbide, described temperature of reaction is 700 ~ 900 DEG C.
Preferably, above-mentionedly prepare in the method steps b of titanium carbide, the proportionlity of described titanium sponge and Faradaic current is that need to control continuous current be 0.2 ~ 0.5A to every gram of titanium sponge.
Preferably, above-mentionedly prepare in the method steps b of titanium carbide, described titanium sponge particle diameter is 5 ~ 10mm.
Preferably, above-mentionedly prepare in the method steps b of titanium carbide, the temperature of described electrolysis is 700 ~ 900 DEG C.
Preferably, above-mentionedly prepare in the method for titanium carbide, whole process is carried out under an inert gas.
Further, above-mentionedly prepare in the method for titanium carbide, described rare gas element is argon gas.
The inventive method can stablize by selecting suitable raw material and electrolysis process the titanium carbide obtaining high purity 99.9% constantly, has that temperature of reaction is low, the reaction times is short, simple operation and other advantages.
Embodiment
Prepare a method for titanium carbide, comprise the following steps:
A, prepare Low-valent Titanium: react in the fused salt of sodium-chlor and Repone K with titanium sponge and titanium tetrachloride and prepare Low-valent Titanium ionogen;
B, prepare titanium carbide: take titanium sponge as anode, graphite is negative electrode, carry out electrolysis in the Low-valent Titanium ionogen of step a after, precipitating metal titanium on negative electrode, can obtain titanium carbide after this metal titanium and graphite react on negative electrode.
The principal reaction equation that the inventive method relates to is:
1) the electrolytical reaction equation of Low-valent Titanium is prepared:
3TiCl
4+Ti＝4TiCl
3
TiCl
4+Ti＝2TiCl
2
2TiCl
3+Ti＝3TiCl
2
TiCl
4+TiCl
2＝2TiCl
3
2) reaction equation of titanium carbide is prepared:
Anode: Ti-2e=Ti
2+
Negative electrode: Ti
2++ 2e=Ti, Ti+C=TiC
As can be seen from above-mentioned 2), carried out two reactions in step b, one is electrolysis, another is that titanium and graphite react, wherein, it is also in Low-valent Titanium ionogen that the graphite on titanium and negative electrode reacts, so the electrolysis temperature of step b is the temperature of reaction of titanium and graphite.
Although market also can buy Low-valent Titanium ionogen, due to himself extremely unstable, easily decompose.And, the Low-valent Titanium ionogen prepared due to the raw material difference of adding is also different, current Low-valent Titanium electrolyte system is configured to main with sodium-chlor, Repone K, also the electrolyte system adopting magnesium chloride, sodium-chlor to form is had, but find through contriver, as the electrolyte system adopting magnesium chloride, sodium-chlor to form, produce magnesium carbide due to side reaction can be there is, thus cause being difficult to obtain titanium carbide.So the electrolyte system that the present invention can only adopt sodium-chlor, Repone K to form.This electrolyte system mainly provides enough temperature for reaction, simultaneously as the carrier of ion migration.Preferably, described sodium-chlor and Repone K by etc. mole to add.Preferably, temperature of reaction is 700 ~ 900 DEG C.
The principle that the inventive method prepares titanium carbide is: in the process of electrolysis, titanium on anode is added in ionogen with the form of ion, under the effect of electrical forces, titanium ion separates out titanium metal at negative electrode, the generation titanium carbide and the graphite of titanium metal and negative electrode reacts.Along with the carrying out of reaction, the titanium carbide that cathode surface generates can stop metal titanium and graphite to react further, so, negative electrode can be taken out from electrolyzer, periodically the titanium carbide that cathode surface generates is scraped, then negative electrode is put into electrolyzer thus proceeds reaction again.
Electrolysis of the present invention adopts the mode of continuous current to carry out electrolysis, and preferably, it is 0.2 ~ 0.5A that every gram of titanium sponge need control continuous current.Then the change by monitoring bath voltage judges the progress of reacting, and generally when bath voltage is without any change, just shows that the titanium carbide that graphite surface generates is more, is just struck off by the titanium carbide of cathode surface, until run out of graphite to change negative electrode again.
In order to slow down the oxidation of graphite and avoid some side reactions; first the air in whole reaction unit is needed to discharge in the inventive method; the mode vacuumized can be adopted; also other modes can be adopted; as long as energy exhausted air, then passes into rare gas element on liquid level and protects whole reaction unit.Preferably, rare gas element is argon gas.
Generate more titanium carbide in order to augmenting response area, the inventive method preferably adopts nickel basketry to carry out splendid attire to titanium sponge.
The titanium ion of separating out due to anode and chlorine fused salt may form Low-valent Titanium, chlorion can be made to discharge and generate chlorine, need the situation of Real-Time Monitoring tail gas in experimentation under certain electric current.
Because product of the present invention only has a kind of solid matter of titanium carbide, its composition measures its Ti, C by chemical means and just can determine whether as product, and wherein titanium content carries out measuring with reference to standard GB/T/T4701.1-2009; C measures with reference to JB/T6647-2011.
Below in conjunction with example, the specific embodiment of the present invention is described further, does not therefore limit the present invention within the scope of described embodiment:
Embodiment 1
Be that the 1Cr18Ni9Ti material crucible of Φ 200 assembles by internal diameter; wherein trim adopts O type fluorine rubber ring; and do water-cooled protection; after equimolar sodium-chlor and potassium chloride mixture are carried out vacuum hydro-extraction process; be warming up to 750 DEG C; at anode frame at the excessive titanium sponge 200g of splendid attire, and pass into the Low-valent Titanium ionogen that titanium tetrachloride reaction obtains 0.5 ~ 1% concentration.
Then the particle diameter again loading onto 60g is that the titanium sponge of 5 ~ 10nm is put in the Low-valent Titanium ionogen of above-mentioned preparation as anode, 6cm in the Low-valent Titanium ionogen of above-mentioned preparation is put under negative electrode graphite rod, be of a size of Φ 16, then be energized and carry out electrolysis at 750 DEG C, treat that bath voltage is stable no longer to change, the reaction times is 2h.Now by anode and cathode lift-off salt face, blowing out is lowered the temperature, and take out and collect the heavy 62g of product, analyzing its result is after testing: 80.8%Ti, 19.2%C, and purity is 99.9%, meet the component proportions of 1 ︰ 1.The electric current of the present embodiment is 26A.
Embodiment 2
Be that the 1Cr18Ni9Ti material crucible of Φ 200 assembles by internal diameter; wherein trim adopts O type fluorine rubber ring; and do water-cooled protection; after equimolar sodium-chlor and potassium chloride mixture are carried out vacuum hydro-extraction process; be warming up to 900 DEG C; at anode frame at the excessive titanium sponge 200g of splendid attire, and pass into the Low-valent Titanium ionogen that titanium tetrachloride reaction obtains 0.5 ~ 1% concentration.
Then the particle diameter again loading onto 80g is that the titanium sponge of 5 ~ 10nm is put in the Low-valent Titanium ionogen of above-mentioned preparation as anode, 6cm in the Low-valent Titanium ionogen of above-mentioned preparation is put under negative electrode graphite rod, be of a size of Φ 16, then be energized and carry out electrolysis at 900 DEG C, treat that scraper process is carried out in the stable no longer change of bath voltage, repeat electrolytic process, until bath voltage is completely constant, now by anode and cathode lift-off salt face, blowing out is lowered the temperature, the heavy 99.4g of product is collected in taking-up, analyzing its result is after testing: 79.7%Ti, 20.3%C, purity is 99.9%, meet the component proportions of 1 ︰ 1.The electric current of the present embodiment is 26A.
Embodiment 3
Be that the 1Cr18Ni9Ti material crucible of Φ 200 assembles by internal diameter; wherein trim adopts O type fluorine rubber ring; and do water-cooled protection; after equimolar sodium-chlor and potassium chloride mixture are carried out vacuum hydro-extraction process; be warming up to 900 DEG C; at anode frame at the excessive titanium sponge 200g of splendid attire, and pass into the Low-valent Titanium ionogen that titanium tetrachloride reaction obtains 0.5 ~ 1% concentration.
Then the particle diameter again loading onto 100g is that the titanium sponge of 5 ~ 10nm is put in the Low-valent Titanium ionogen of above-mentioned preparation as anode, 5cm in the Low-valent Titanium ionogen of above-mentioned preparation is put under negative electrode graphite rod, be of a size of Φ 16, then be energized and carry out electrolysis at 900 DEG C, treat that scraper process is carried out in the stable no longer change of bath voltage, repeat electrolytic process, until bath voltage is completely constant, now by anode and cathode lift-off salt face, blowing out is lowered the temperature, the heavy 112.8g of product is collected in taking-up, analyzing its result is after testing: 79.9%Ti, 20.1%C, purity is 99.9%, meet the component proportions of 1 ︰ 1.The electric current of the present embodiment is 26A.
Claims (8)
1. prepare a method for titanium carbide, it is characterized in that: comprise the following steps:
A, prepare Low-valent Titanium: react in the fused salt of sodium-chlor and Repone K with titanium sponge and titanium tetrachloride and prepare Low-valent Titanium ionogen;
B, prepare titanium carbide: take titanium sponge as anode, graphite is negative electrode, carry out electrolysis in the Low-valent Titanium ionogen of step a after, precipitating metal titanium on negative electrode, can obtain titanium carbide after this metal titanium and graphite react on negative electrode.
2. the method preparing titanium carbide according to claim 1, is characterized in that: in step a, described sodium-chlor and Repone K with etc. mole to add.
3. the method preparing titanium carbide according to claim 1, is characterized in that: in step a, and described temperature of reaction is 700 ~ 900 DEG C.
4. the method preparing titanium carbide according to claim 1, is characterized in that: in step b, and the proportionlity of described titanium sponge and Faradaic current is that need to control continuous current be 0.2 ~ 0.5A to every gram of titanium sponge.
5. the method preparing titanium carbide according to claim 1, is characterized in that: in step b, and described titanium sponge particle diameter is 5 ~ 10mm.
6. the method preparing titanium carbide according to claim 1, is characterized in that: in step b, and the temperature of described electrolysis is 700 ~ 900 DEG C.
7. the method preparing titanium carbide according to claim 1, is characterized in that: whole process is carried out under an inert gas.
8. the method preparing titanium carbide according to claim 7, is characterized in that: described rare gas element is argon gas.
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Cited By (6)
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| CN109231209A (en) * | 2018-10-30 | 2019-01-18 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of titanium carbide |
| RU2687423C1 (en) * | 2018-09-26 | 2019-05-13 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Method of producing titanium carbide-based powder |
| CN110304653A (en) * | 2019-07-12 | 2019-10-08 | 北京科技大学 | A kind of surface modifying method of titanium carbide granule |
| CN110512233A (en) * | 2019-09-25 | 2019-11-29 | 武汉大学 | A kind of porous carbide hydrogen-precipitating electrode and one one-step preparation method with honeycomb microstructure |
| CN111039290A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院金属研究所 | Method for preparing transition metal carbide powder in situ by molten salt disproportionation reaction |
| CN115161714A (en) * | 2022-08-01 | 2022-10-11 | 青岛国韬钛金属产业研究院有限公司 | Method for preparing metal titanium by molten salt solid-state deoxidation method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2687423C1 (en) * | 2018-09-26 | 2019-05-13 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" | Method of producing titanium carbide-based powder |
| CN111039290A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院金属研究所 | Method for preparing transition metal carbide powder in situ by molten salt disproportionation reaction |
| CN109231209A (en) * | 2018-10-30 | 2019-01-18 | 攀钢集团攀枝花钢铁研究院有限公司 | The preparation method of titanium carbide |
| CN110304653A (en) * | 2019-07-12 | 2019-10-08 | 北京科技大学 | A kind of surface modifying method of titanium carbide granule |
| CN110304653B (en) * | 2019-07-12 | 2021-02-02 | 北京科技大学 | Surface modification method of titanium carbide particles |
| CN110512233A (en) * | 2019-09-25 | 2019-11-29 | 武汉大学 | A kind of porous carbide hydrogen-precipitating electrode and one one-step preparation method with honeycomb microstructure |
| CN115161714A (en) * | 2022-08-01 | 2022-10-11 | 青岛国韬钛金属产业研究院有限公司 | Method for preparing metal titanium by molten salt solid-state deoxidation method |
| CN115161714B (en) * | 2022-08-01 | 2023-07-18 | 青岛国韬钛金属产业研究院有限公司 | Method for preparing metallic titanium by molten salt solid-state deoxidization method |
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